EP2820188A1 - Novel method for producing paper implementing a base copolymer having reacted with an aldehyde as a dry strength, retention, drainage and machinability agent - Google Patents

Novel method for producing paper implementing a base copolymer having reacted with an aldehyde as a dry strength, retention, drainage and machinability agent

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Publication number
EP2820188A1
EP2820188A1 EP13712850.0A EP13712850A EP2820188A1 EP 2820188 A1 EP2820188 A1 EP 2820188A1 EP 13712850 A EP13712850 A EP 13712850A EP 2820188 A1 EP2820188 A1 EP 2820188A1
Authority
EP
European Patent Office
Prior art keywords
polymer
group
acid
aldehyde
base
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP13712850.0A
Other languages
German (de)
French (fr)
Other versions
EP2820188B1 (en
Inventor
René Hund
Cyril BARRIERE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SPCM SA
Original Assignee
SPCM SA
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Filing date
Publication date
Application filed by SPCM SA filed Critical SPCM SA
Publication of EP2820188A1 publication Critical patent/EP2820188A1/en
Application granted granted Critical
Publication of EP2820188B1 publication Critical patent/EP2820188B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D21H17/375—Poly(meth)acrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/28—Condensation with aldehydes or ketones
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/56—Polyamines; Polyimines; Polyester-imides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/72—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic material
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages

Definitions

  • the invention relates to a novel paper-making process which uses as a dry strength, retention, dewatering and machinability agent a product resulting from the reaction between at least one aldehyde and at least one ( co) cationic or amphoteric base polymer, said copolymer comprising acrylamide or derivative and incorporating, within itself, at least one polyfunctional compound comprising at least 3 heteroatoms, of which at least 3 of these heteroatoms each have at least one mobile hydrogen .
  • WO2011 / 15783 describes polymers obtained by Hofmann degradation reaction on a (co) polymer base.
  • the base copolymer contains a polyfunctional compound incorporated at the time of polymerization of the (co) polymer base. These compounds are used in papermaking as a flocculation, retention and / or drainage agent.
  • US20110056640 discloses a papermaking process using a compound resulting from the reaction between an aldehyde and an acrylamide / diallyldimethylammonium chloride copolymer. This process only improves drainage.
  • WO2010 / 059946 and US2006 / 0270801 disclose a mixture of compounds for improving paper strength. These mixtures comprise a glyoxalated polymer, and optionally a polyfunctional compound.
  • the document WO2005 / 072185 describes a process for producing paper using a polymer whose amine or amide functions have reacted with an aldehyde.
  • WO2007 / 041380 discloses a wet strength agent consisting of a mixture of glyoxalated polymers.
  • the problem to be solved by the invention is to develop a novel papermaking process in which both the dewatering properties and the physical properties of the paper are improved. Description of the invention
  • the Applicant has found and developed a novel method of manufacturing a sheet of paper and / or cardboard and the like, according to which, before or after forming said sheet, the cellulosic material is brought into contact with at least one additive .
  • the process is characterized in that said additive is a cationic or amphoteric (co) polymer derived from the reaction between at least one aldehyde and at least one (co) polymer base comprising at least one nonionic monomer chosen from the group comprising acrylamide (and / or methacrylamide), N, N-dimethylacrylamide, and / or acrylonitrile, said base copolymer being previously modified with at least one polyfunctional compound comprising at least 3 heteroatoms chosen from N, S, O, P, at least 3 of these heteroatoms each have at least one mobile hydrogen.
  • the modification of the (co) polymer base with at least one additional polyfunctional compound consists either of incorporating the additional polyfunctional compound (s) before or during the polymerization of the constituent comonomers. of the (co) polymer base, or to graft the additional polyfunctional compound (s) onto the (co) polymer base.
  • the polyfunctional compound when the polyfunctional compound is incorporated before or during the polymerization, it does not react with the nonionic monomer chosen from the group comprising acrylamide (and / or methacrylamide), N, N dimethylacrylamide, and / or acrylonitrile. Indeed, the nonionic monomer is added while the reaction medium is in the polymerization conditions.
  • the polyfunctional compounds may be: oligomers, polymers, carbon chains having at least three carbon atoms.
  • the polyfunctional compound may be a polymer resulting from the polymerization called "template”. These are polymers in which are introduced during their synthesis, a low molecular weight polymer that will absorb one of the monomers entering the polymerization.
  • the so-called additional polyfunctional compounds are chosen from the group comprising polyethyleneimines (PEI), polyamines (primary and secondary), polyallyamines, polythiols, polyalcohols, polyamides epichlorohydrin (PAE), polyamines amides (PAA)
  • the cationic or amphoteric final (co) polymer therefore comprises at least one nonionic monomer chosen from the group comprising acrylamide (and / or methacrylamide), N, N-dimethylacrylamide and / or acrylonitrile, and is modified, prior to the reaction with an aldehyde compound, at least one additional polymer selected from the group consisting of polyethyleneimine, polyamine (primary or secondary), polyallylamine, polythiols, polyalcohols, polyamides epichlorohydrin (PAE), polyamines amides (PAA).
  • the incorporated polyfunctional compound is selected from the group consisting of polyethyleneimine (PEI) and polyamine amide (PAA).
  • the (co) polymer base contains at least 100 ppm of polyfunctional polymer, preferably at least 500 ppm, more preferably at least 1000 ppm.
  • the aldehyde may be chosen from the group comprising glyoxal, glutaraldehyde, furan-dialdehyde, 2-hydroxyadipaldehyde, succinaldehyde, dialdehyde starch, 2,2-dimethoxyethanal, diepoxy compounds, and combinations thereof.
  • the aldehyde compound will be glyoxal.
  • the (co) base polymer is branched by means of a radical branching agent.
  • the resulting copolymer is reacted with glyoxal.
  • the branching may preferably be carried out during the polymerization of the base copolymer, in the presence of a polyfunctional radical branching agent and optionally of a transfer agent.
  • branching agents methylene bisacrylamide (MBA), ethylene glycol di-acrylate, polyethylene glycol dimethacrylate, diacrylamide, cyanomethylacrylate, vinyloxyethylacrylate or methacrylate, triallylamine,
  • the branching agent is advantageously introduced at a rate of from five to fifty thousand (5 to 50,000) parts per million by weight relative to the active ingredient, preferably from 5 to 10,000, advantageously from 5 to 5,000.
  • the branching agent is methylenebisacrylamide (MBA).
  • transfer agents isopropyl alcohol, sodium hypophosphite, mercaptoethanol, etc.
  • the process can be used successfully for the manufacture of paper and paperboard packaging, paper coating media, sanitary and household papers, of any type of paper, paperboard or the like requiring the use of a polymer as a dry strength, retention, dewatering and machinability agent. Machinability means optimizing the operation of the paper machine by increasing productivity by better dripping on the table, better dryness at the press section, a reduction of breakages by a cleaner circuits and a decrease deposits.
  • the method also makes it possible to obtain good drainage properties and good physical properties (improvement of bursting, breaking length, ring crush test, short span compression test, concora medium test, internal cohesion, wet break length).
  • the final cationic or amphoteric copolymer used in the process of the invention has a cationic charge density preferably greater than 0.4 meq / g and advantageously greater than 1.25 meq / g.
  • the cationic or amphoteric (co) polymer is derived from the reaction between: 1 to 30% by weight of at least one aldehyde preferably chosen from the group comprising glyoxal, glutaraldehyde, furan-dialdehyde, 2- hydroxyadipaldehyde, succinaldehyde, dialdehyde starch, 2,2-dimethoxyethanal, diepoxy compounds, and combinations thereof,
  • a nonionic monomer chosen from the group comprising acrylamide (and / or methacrylamide), N, N-dimethylacrylamide and / or acrylonitrile, preferably acrylamide, at least 100 ppm at least one additional polyfunctional compound chosen from the group comprising polyethyleneimine, polyamine (primary or secondary), polyallylamine, polythiols, polyalcohols, polyamides epichlorohydrin (PAE), polyamines amides (PAA) advantageously polyethyleneimine,
  • o optionally at least:
  • unsaturated cationic ethylenic monomer preferably selected from the group consisting of dialkylaminoalkyl (meth) acrylamide, diallylamine, methyldiallylamine and their quaternary ammonium or acid salts.
  • dialkylaminoalkyl (meth) acrylamide diallylamine
  • methyldiallylamine methyldiallylamine
  • their quaternary ammonium or acid salts quaternary ammonium or acid salts.
  • DMAC dimethyldiallylammonium chloride
  • APITAC acrylamidopropyltrimethylammonium chloride
  • MATAC methacrylamidopropyltrimethylammonium chloride
  • ⁇ and / or a nonionic monomer preferably selected from the group consisting of N-vinyl acetamide, N-vinylformamide, N-vinylpyrrolidone and / or vinyl acetate, ⁇ and / or an anionic monomer or acid anhydride selected from the group consisting of (meth) acrylic acid, sulfonic acrylamidomethylpropyl acid, itaconic acid, maleic anhydride, maleic acid, methallyl acid sulfonic acid, vinylsulfonic acid and their salts.
  • the final cationic or amphoteric (co) polymer is derived from the reaction preferably:
  • a radical branching agent by means of a radical branching agent and comprising:
  • At least one unsaturated cationic ethylenic comonomer selected from the group consisting of dialkylaminoalkyl (meth) acrylamide, diallylamine, methyldiallylamine and their quaternary ammonium or acid salt monomers, preferably dimethyldiallylammonium chloride,
  • water-insoluble monomers such as acrylic, allylic or vinyl monomers having a hydrophobic group.
  • these monomers will be used in very small amounts, less than 20 mole%, preferably less than 10 mole%, and they will be chosen preferentially from the group comprising acrylamide derivatives such as N-alkylacrylamide by for example N-tert-butylacrylamide, octylacrylamide and ⁇ , ⁇ -dialkylacrylamides such as ⁇ , ⁇ -dihexylacrylamide ... acrylic acid derivatives such as alkyl acrylates and methacrylates ...
  • the base copolymer used in the invention is a copolymer of a nonionic monomer and a cationic monomer.
  • the incorporation of the additional polyfunctional compound modifying the structure of the (co) polymer base can be done in the reaction medium before or during polymerization, or by any other grafting method on the finished base copolymer.
  • the polyfunctional compound does not react with the monomers until they are polymerized.
  • the additional polyfunctional compound will be mixed with a comonomer before polymerization.
  • the amount of final (co) polymer introduced into the fibrous suspension is between 500 and 4000 grams of active polymer per tonne of dry pulp (g / t).
  • the quantity introduced is between 1000 g / t and 3000 g / t.
  • the (co) polymer base does not require the development of a particular polymerization process.
  • the main polymerization techniques are: precipitation polymerization, emulsion polymerization (aqueous or inverse) followed or not by a distillation step and / or spray drying, and suspension polymerization or solution polymerization, both of which are preferred.
  • Glyoxalation does not require any particular method.
  • the main glyoxalation techniques known to those skilled in the art can be used.
  • the pH may be adjusted after addition of glyoxal with a sodium hydroxide solution. It is also possible to conduct the reaction at controlled pH by continuous addition of sodium hydroxide, but also to add the glyoxal in several fractions. The progress of the reaction may also be followed by a measurement of viscosity, turbidity, etc.
  • the additive is added to the process, before or after forming the sheet.
  • the contacting of the cellulosic material with the additive can be carried out in different ways.
  • the final (co) polymer may be used as a dilute or undiluted aqueous solution. It will be added to the cellulosic material. It may be applied by an impregnation technique, or may be added directly to the fibrous suspension at any point in the papermaking process where usually dry strength agents are introduced. It can be introduced into thick stock or thin stock. It can be added at the level of the fan pump or the headbox. Preferably the (co) polymer will be introduced before the headbox. It may also be at the level of the training table or press size, for example by spray.
  • the final (co) polymer is injected industrially into the fibrous suspension, i.e. before dilution with white water (thick paste).
  • concentrations of the dough are of the order of 3% and 5%.
  • the process can be used with virgin fiber pulps (Kraft, Bisulfite ..), recycled fibers, de-inked pastes, mechanical and thermo mechanical pulps.
  • the final (co) polymer may be prepared near the paper machine.
  • the polymers of the invention identified among polymers 1 to 17 were obtained from a PEI-modified base copolymer during polymerization according to the following protocol .
  • the examples were carried out with a copolymer acrylamide and dimethyldiallyl ammonium chloride (DADMAC), branched with MBA (1000 ppm / active ingredient), modified with a polyethyleneimine polymer (BASF type Polymin HM), up to 1% compared to the active ingredient.
  • DADMAC dimethyldiallyl ammonium chloride
  • MBA 1000 ppm / active ingredient
  • BASF type Polymin HM polyethyleneimine polymer
  • the acrylamide will be incorporated in continuous casting for 2 hours, in a reaction medium maintained at 85 ° C.
  • Catalysis will be SPS and MBS, catalysts well known to those skilled in the art.
  • the examples (polymers 19 and 20) were carried out in the same manner as above, with the difference that the polyethyleneimine is not mixed with the monomer in the reactor. To do this, the polyethyleneimine is added to the reactor after the polymerization at a level of 1% relative to the active ingredient.
  • the grafting is by catalysis using 1500 ppm of SPS in continuous casting for lh30.
  • the pH can be adjusted after adding glyoxal with 10% sodium hydroxide solution. It is possible to conduct the reaction at controlled pH by continuous addition of 10% sodium hydroxide, but also to add the glyoxal in several fractions.
  • the viscometer used is Brookfield type, with a LV1 module and a speed of 60 rpm. Preparation of the dough
  • the paste used consists of recycled cardboard fibers.
  • the pulp is prepared by disintegrating for 90 minutes 90 grams of recycled fibers in 2 liters of hot water.
  • the Shopper degree of the dough thus obtained is 43.
  • the tests are carried out with the paste at neutral pH.
  • the paste obtained is then diluted to a total volume of 9 liters. Once the consistency measured accurately, the necessary amount of this paste is taken so as to ultimately obtain a sheet with a basis weight of 120g / m2.
  • T 30s: Stopping the agitation and recovery of the liter of dough. Realization of the TAPPI T 2270M-94 test.
  • the paper forms are made with an automatic dynamic form.
  • the paste is introduced into the cuvier of the dynamic form, diluted to a consistency of 0.32% and stirred moderately with a mechanical stirrer to homogenize the fibrous suspension.
  • the dough is pumped to the nozzle level to prime the circuit.
  • a blotter and training cloth are placed in the bowl of the dynamic formette before starting the rotation of the bowl at 900m / min and constructing the water wall.
  • the final copolymer is then introduced into the stirred fibrous suspension with a contact time of 30 seconds.
  • the sheet is then made (in automatic mode) by 22 round-trips of the nozzle projecting the paste in the wall of water.
  • the forming web with the formed fiber network is removed from the dynamically shaped bowl and placed on a table.
  • a dry blotter is deposited on the side of the wet fiber mat and is pressed once with a roll. The whole is returned and the fabric is delicately separated from the fibrous mat.
  • a second dry blotter is deposited and the sheet (between the two blotters) is pressed once under a press delivering 4 bars and is then dried on a dryer stretched for 9 min at 107 ° C. The two blotters are then removed and the sheet is stored overnight in a room with controlled humidity and temperature (50% relative humidity and 23 ° C). The dry strength properties of all the sheets obtained by this procedure are then evaluated.
  • Burst test Burst index is measured with a Messmer Buchel M 405 burst (average of 14 measurements). The test is performed according to TAPPI standard T403 OM 91
  • the sheets of paper are made according to the above procedure by introducing the final copolymer at a dosage of 2.5 kg / T (dry polymer / dry fiber).
  • the branching alone of the glyoxalated base copolymer and free of PEI (polymer 3) makes it possible to obtain an improvement in drainage performance, but is detrimental to the improvement of the physical properties.
  • the method of the invention makes it possible to obtain an improvement of drainage superior to other products while maintaining or even while improving the dry physical properties.
  • the table above shows the evolution of the results with respect to the increase of the cationicity of the base polymer.
  • the polymers of the invention are all better than the polymer 9.
  • polymers 10 and 14 exhibit different performance.
  • Polymer 14 which has a cationicity of 40 mole%, gives superior results whether in drip or burst (Burst Index) to polymer 10 (5 mole% cationicity).
  • the polymer 17 corresponds to Example 7 of the patent US20110056640 which was reproduced and then tested.
  • Polymers 19 and 20 were made from the (co) polymer base with post-grafting of PEI. More specifically, the polymerization of acrylamide and DADMAC is carried out in the presence of MBA. The polymer obtained is then separated into three fractions.
  • the first fraction reacts with glyoxal as previously described: Sample 18.
  • PEI and an initiator are added in continuous casting for 90 minutes at 80 ° C for the purpose of post-grafting the PEI.
  • SPS initiator
  • the third fraction was treated in the same way as for sample 19, but without the addition of PEI.
  • the goal is to evaluate the impact of the continuous addition of the SPS. Gloxalation is identical to Examples 18 and 19.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paper (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A method for producing a sheet of paper and/or cardboard and the like, according to which the cellulosic material is brought into contact with at least one dry strength agent, characterised in that said agent is a cationic or amphoteric (co)polymer resulting from the reaction between at least one aldehyde and at least one base (co)polymer comprising at least one non-ionic monomer, said base copolymer being previously modified with at least one polyfunctional compound comprising at least 3 heteroatoms chosen from N, S, O, P, whereof at least 3 of said heteroatoms each have at least one mobile hydrogen atom.

Description

NOUVEAU PROCEDE DE FABRICATION DE PAPIER METTANT EN OEUVRE UN COPOLYMERE BASE AYANT REAGI AVEC UN ALDEHYDE COMME AGENT DE RESISTANCE A SEC, DE RETENTION, D'EGOUTTAGE ET DE MACHINABILITE  NOVEL PAPERMAKING PROCESS USING A BASIC COPOLYMER HAVING REACTED WITH ALDEHYDE AS DRY RESISTANCE, RETENTION, DRIP, AND MACHINABILITY AGENT
L'invention concerne un nouveau procédé de fabrication de papier mettant en œuvre en tant qu'agent de résistance à sec, de rétention, d'égouttage et de machinabilité, un produit issu de la réaction entre au moins un aldéhyde et au moins un (co)polymère base cationique ou amphotère, ledit copolymère comprenant de l'acrylamide ou dérivé et incorporant, en son sein même, au moins un composé polyfonctionnel comprenant au moins 3 hétéroatomes, dont au moins 3 de ces hétéroatomes présentent chacun au moins un hydrogène mobile. The invention relates to a novel paper-making process which uses as a dry strength, retention, dewatering and machinability agent a product resulting from the reaction between at least one aldehyde and at least one ( co) cationic or amphoteric base polymer, said copolymer comprising acrylamide or derivative and incorporating, within itself, at least one polyfunctional compound comprising at least 3 heteroatoms, of which at least 3 of these heteroatoms each have at least one mobile hydrogen .
Le document WO2011/15783 du Demandeur décrit des polymères obtenus par réaction de dégradation d'Hofmann sur un (co)polymère base. Le copolymère base contient un composé polyfonctionnel incorporé au moment de la polymérisation du (co)polymère base. Ces composés sont utilisés dans la fabrication du papier en tant qu'agent de floculation, de rétention et/ou de drainage. Le document US20110056640 décrit un procédé de fabrication de papier mettant en oeuvre un composé issu de la réaction entre un aldéhyde et un copolymère acrylamide/chlorure de diallyldimethyl ammonium. Ce procédé n'améliore que le drainage. Les documents WO2010/059946 et US2006/0270801 décrivent un mélange de composés permettant d'améliorer la résistance du papier. Ces mélanges comprennent un polymère glyoxalé, et éventuellement un composé polyfonctionnel. The Applicant's document WO2011 / 15783 describes polymers obtained by Hofmann degradation reaction on a (co) polymer base. The base copolymer contains a polyfunctional compound incorporated at the time of polymerization of the (co) polymer base. These compounds are used in papermaking as a flocculation, retention and / or drainage agent. US20110056640 discloses a papermaking process using a compound resulting from the reaction between an aldehyde and an acrylamide / diallyldimethylammonium chloride copolymer. This process only improves drainage. WO2010 / 059946 and US2006 / 0270801 disclose a mixture of compounds for improving paper strength. These mixtures comprise a glyoxalated polymer, and optionally a polyfunctional compound.
Le document WO2005/072185 décrit un procédé de fabrication du papier mettant en œuvre un polymère dont les fonctions aminé ou amide ont réagi avec un aldéhyde. The document WO2005 / 072185 describes a process for producing paper using a polymer whose amine or amide functions have reacted with an aldehyde.
Le document WO2007/041380 décrit un agent de résistance humide consistant en un mélange de polymères glyoxalés. Le problème que se propose de résoudre l'invention est de mettre au point un nouveau procédé de fabrication de papier dans lequel à la fois les propriétés d'égouttage et les propriétés physiques du papier sont améliorées. Description de l'invention WO2007 / 041380 discloses a wet strength agent consisting of a mixture of glyoxalated polymers. The problem to be solved by the invention is to develop a novel papermaking process in which both the dewatering properties and the physical properties of the paper are improved. Description of the invention
Le Demandeur a trouvé et mis au point un nouveau procédé de fabrication d'une feuille de papier et/ou de carton et analogues, selon lequel, avant ou après formation de ladite feuille, on met en contact la matière cellulosique avec au moins un additif. The Applicant has found and developed a novel method of manufacturing a sheet of paper and / or cardboard and the like, according to which, before or after forming said sheet, the cellulosic material is brought into contact with at least one additive .
Le procédé se caractérise en ce que ledit additif est un (co)polymère cationique ou amphotère issu de la réaction entre au moins un aldéhyde et au moins un (co)polymère base comprenant au moins un monomère non ionique choisi dans le groupe comprenant l'acrylamide (et/ou le méthacrylamide), le N,N diméthylacrylamide, et/ou l'acrylonitrile, ledit copolymère base étant préalablement modifié avec au moins un composé polyfonctionnel comprenant au moins 3 hétéroatomes choisis parmi N, S, O, P, dont au moins 3 de ces hétéroatomes présentent chacun au moins un hydrogène mobile. Dans la suite de la description et dans les revendications, on désigne : The process is characterized in that said additive is a cationic or amphoteric (co) polymer derived from the reaction between at least one aldehyde and at least one (co) polymer base comprising at least one nonionic monomer chosen from the group comprising acrylamide (and / or methacrylamide), N, N-dimethylacrylamide, and / or acrylonitrile, said base copolymer being previously modified with at least one polyfunctional compound comprising at least 3 heteroatoms chosen from N, S, O, P, at least 3 of these heteroatoms each have at least one mobile hydrogen. In the remainder of the description and in the claims, reference is made to:
- par additif, un agent à la fois de résistance à sec, de rétention, d'égouttage et de machinabilité,  - by additive, an agent at the same time of dry resistance, retention, dewatering and machinability,
par (co)polymère base, le (co)polymère avant la réaction avec le composé aldéhyde,  by (co) polymer base, the (co) polymer before the reaction with the aldehyde compound,
- par (co)polymère final, le produit issu de la réaction entre le composé aldéhyde et le (co)polymère base.  by final (co) polymer, the product resulting from the reaction between the aldehyde compound and the (co) polymer base.
Selon l'invention, la modification du (co)polymère base avec au moins un composé polyfonctionnel additionnel consiste soit à incorporer le(s) composé(s) polyfonctionnel(s) additionnel(s) avant ou pendant la polymérisation des co- monomères constitutifs du (co)polymère base, soit à greffer le(s) composé(s) polyfonctionnel(s) additionnel(s) sur le (co)polymère base. De manière avantageuse, lorsque le composé polyfonctionnel est incorporé avant ou pendant la polymérisation, il ne réagit pas avec le monomère non ionique choisi dans le groupe comprenant l'acrylamide (et/ou le méthacrylamide), le N,N diméthylacrylamide, et/ou l'acrylonitrile. En effet, le monomère non ionique est ajouté alors que le milieu réactionnel est dans les conditions de polymérisation. According to the invention, the modification of the (co) polymer base with at least one additional polyfunctional compound consists either of incorporating the additional polyfunctional compound (s) before or during the polymerization of the constituent comonomers. of the (co) polymer base, or to graft the additional polyfunctional compound (s) onto the (co) polymer base. Advantageously, when the polyfunctional compound is incorporated before or during the polymerization, it does not react with the nonionic monomer chosen from the group comprising acrylamide (and / or methacrylamide), N, N dimethylacrylamide, and / or acrylonitrile. Indeed, the nonionic monomer is added while the reaction medium is in the polymerization conditions.
Les composés polyfonctionnels peuvent être : oligomères, polymères, chaînes carbonées comportant au moins trois atomes de carbone. Le composé polyfonctionnel peut être un polymère issu de la polymérisation dite « template ». Il s'agit de polymères dans lesquels sont introduits, lors de leur synthèse, un polymère de bas poids moléculaire qui absorbera un des monomères entrant dans la polymérisation. En particulier, les composés polyfonctionnels dits additionnels sont choisis dans le groupe comprenant les polyethylèneimines (PEI), les polyamines (primaires et secondaires), les polyallyamines, les polythiols, les polyalcools, les polyamides epichlorhydrine (PAE), les polyamines amides (PAA), Le (co)polymère final cationique ou amphotère comprend donc au moins un monomère non ionique choisi dans le groupe comprenant l'acrylamide (et/ou le méthacrylamide), le N,N diméthylacrylamide et/ou l'acrylonitrile, et est modifié, préalablement à la réaction avec un composé aldéhyde, par au moins un polymère additionnel choisi dans le groupe comprenant polyéthylèneimine, polyamine (primaire ou secondaire), polyallylamine, polythiols, polyalcools, polyamides epichlorhydrine (PAE), polyamines amides (PAA). The polyfunctional compounds may be: oligomers, polymers, carbon chains having at least three carbon atoms. The polyfunctional compound may be a polymer resulting from the polymerization called "template". These are polymers in which are introduced during their synthesis, a low molecular weight polymer that will absorb one of the monomers entering the polymerization. In particular, the so-called additional polyfunctional compounds are chosen from the group comprising polyethyleneimines (PEI), polyamines (primary and secondary), polyallyamines, polythiols, polyalcohols, polyamides epichlorohydrin (PAE), polyamines amides (PAA) The cationic or amphoteric final (co) polymer therefore comprises at least one nonionic monomer chosen from the group comprising acrylamide (and / or methacrylamide), N, N-dimethylacrylamide and / or acrylonitrile, and is modified, prior to the reaction with an aldehyde compound, at least one additional polymer selected from the group consisting of polyethyleneimine, polyamine (primary or secondary), polyallylamine, polythiols, polyalcohols, polyamides epichlorohydrin (PAE), polyamines amides (PAA).
Dans un mode de réalisation préférentiel, le composé polyfonctionnel incorporé est choisi dans le groupe comprenant la polyéthylèneimine (PEI) et la polyamine amide (PAA). In a preferred embodiment, the incorporated polyfunctional compound is selected from the group consisting of polyethyleneimine (PEI) and polyamine amide (PAA).
En pratique, le (co)polymère base contient au moins 100 ppm de polymère polyfonctionnel, de préférence au moins 500 ppm, de manière plus avantageuse au moins 1000 ppm. Avantageusement, l'aldéhyde pourra être choisi dans le groupe comprenant le glyoxal, le glutaraldéhyde, le furane-dialdéhyde, le 2-hydroxyadipaldéhyde, le succinaldéhyde, le dialdéhyde amidon, le 2,2 dimethoxyethanal, les composés diépoxy, et leurs combinaisons. De préférence le composé aldéhyde sera le glyoxal. In practice, the (co) polymer base contains at least 100 ppm of polyfunctional polymer, preferably at least 500 ppm, more preferably at least 1000 ppm. Advantageously, the aldehyde may be chosen from the group comprising glyoxal, glutaraldehyde, furan-dialdehyde, 2-hydroxyadipaldehyde, succinaldehyde, dialdehyde starch, 2,2-dimethoxyethanal, diepoxy compounds, and combinations thereof. Preferably the aldehyde compound will be glyoxal.
Selon une caractéristique préférée de l'invention, le (co)polymère base est ramifié au moyen d'un agent ramifiant radicalaire. Dans ce cas, on fait réagir le copolymère obtenu avec le glyoxal. On pourra effectuer la ramification de préférence durant la polymérisation du copolymère base, en présence d'un agent ramifiant radicalaire polyfonctionnel et éventuellement d'un agent de transfert. On trouvera ci dessous une liste non limitative des ramifiants : méthylène bisacrylamide (MBA), l'ethylene glycol di-acrylate, le polyethylene glycol dimethacrylate, le diacrylamide, le cyanomethylacrylate, le vinyloxyethylacrylate ou methacrylate, la triallylamine, According to a preferred feature of the invention, the (co) base polymer is branched by means of a radical branching agent. In this case, the resulting copolymer is reacted with glyoxal. The branching may preferably be carried out during the polymerization of the base copolymer, in the presence of a polyfunctional radical branching agent and optionally of a transfer agent. The following is a nonlimiting list of branching agents: methylene bisacrylamide (MBA), ethylene glycol di-acrylate, polyethylene glycol dimethacrylate, diacrylamide, cyanomethylacrylate, vinyloxyethylacrylate or methacrylate, triallylamine,
En pratique, l'agent de ramification est introduit avantageusement à raison de cinq à cinquante milles (5 à 50000) parties par million en poids par rapport à la matière active, de préférence 5 à 10000, avantageusement de 5 à 5000. Avantageusement, l'agent de ramification est le méthylène bis acrylamide (MBA). In practice, the branching agent is advantageously introduced at a rate of from five to fifty thousand (5 to 50,000) parts per million by weight relative to the active ingredient, preferably from 5 to 10,000, advantageously from 5 to 5,000. Advantageously, the branching agent is methylenebisacrylamide (MBA).
On trouvera ci-dessous une liste non limitative des agents de transfert : alcool isopropylique, hypophosphite de sodium, mercaptoethanol, etc .. Le procédé pourra être utilisé avec succès pour la fabrication de papiers et cartons d'emballage, de papiers supports de couchage, papiers sanitaires et domestiques, de tout type de papiers, cartons ou analogues nécessitant l'utilisation d'un polymère comme agent de résistance à sec, de rétention, d'égouttage et de machinabilité. Par machinabilité, on désigne l'optimisation du fonctionnement de la machine à papier en augmentant la productivité par un meilleur égouttage sur la table, une meilleure siccité à la section de presse, une diminution des casses par une plus grande propreté des circuits et une diminution des dépôts. Le procédé permet par ailleurs d'obtenir de bonnes propriétés d'égouttage et de bonnes propriétés physiques (amélioration de l'éclatement, de la longueur de rupture, du ring crush test, du short span compression test, du concora médium test, de la cohésion interne, de la longueur de rupture humide). Below is a non-exhaustive list of transfer agents: isopropyl alcohol, sodium hypophosphite, mercaptoethanol, etc. The process can be used successfully for the manufacture of paper and paperboard packaging, paper coating media, sanitary and household papers, of any type of paper, paperboard or the like requiring the use of a polymer as a dry strength, retention, dewatering and machinability agent. Machinability means optimizing the operation of the paper machine by increasing productivity by better dripping on the table, better dryness at the press section, a reduction of breakages by a cleaner circuits and a decrease deposits. The method also makes it possible to obtain good drainage properties and good physical properties (improvement of bursting, breaking length, ring crush test, short span compression test, concora medium test, internal cohesion, wet break length).
De même, le copolymère cationique ou amphotère final mis en œuvre dans le procédé de l'invention a une densité de charge cationique de préférence supérieure à 0,4 meq/g et avantageusement supérieure à 1,25 meq/g. Similarly, the final cationic or amphoteric copolymer used in the process of the invention has a cationic charge density preferably greater than 0.4 meq / g and advantageously greater than 1.25 meq / g.
En pratique, le (co)polymère cationique ou amphotère est issu de la réaction entre: de 1 à 30% massique d'au moins un aldéhyde choisi préférentiellement dans le groupe comprenant le glyoxal, le glutaraldéhyde, le furane-dialdéhyde, le 2- hydroxyadipaldéhyde, le succinaldéhyde, le dialdéhyde amidon, le 2,2 dimethoxyethanal, les composés diépoxy, et leurs combinaisons, In practice, the cationic or amphoteric (co) polymer is derived from the reaction between: 1 to 30% by weight of at least one aldehyde preferably chosen from the group comprising glyoxal, glutaraldehyde, furan-dialdehyde, 2- hydroxyadipaldehyde, succinaldehyde, dialdehyde starch, 2,2-dimethoxyethanal, diepoxy compounds, and combinations thereof,
avec au moins un (co)polymère base éventuellement ramifié au moyen d'un agent ramifiant radicalaire et contenant :  with at least one (co) polymer base optionally branched by means of a radical branching agent and containing:
o au moins 5 moles % d'un monomère non ionique choisi dans le groupe comprenant l'acrylamide (et/ou le méthacrylamide), le N, N diméthylacrylamide et/ou l'acrylonitrile, préférentiellement l'acrylamide, o au moins 100 ppm d'au moins un composé polyfonctionnel additionnel choisi dans le groupe comprenant polyéthylèneimine, polyamine (primaire ou secondaire), polyallylamine, polythiols, les polyalcools, polyamides epichlorhydrine (PAE), polyamines amides (PAA) avantageusement polyéthylèneimine,  at least 5 mole% of a nonionic monomer chosen from the group comprising acrylamide (and / or methacrylamide), N, N-dimethylacrylamide and / or acrylonitrile, preferably acrylamide, at least 100 ppm at least one additional polyfunctional compound chosen from the group comprising polyethyleneimine, polyamine (primary or secondary), polyallylamine, polythiols, polyalcohols, polyamides epichlorohydrin (PAE), polyamines amides (PAA) advantageously polyethyleneimine,
o optionnellement au moins :  o optionally at least:
un monomère éthylénique cationique non saturé, choisi préférentiellement dans le groupe comprenant les monomères de type dialkylaminoalkyl (meth)acrylamide, diallylamine, methyldiallylamine et leurs sel d'ammonium quaternaire ou d'acides. On citera en particulier le chlorure de dimethyldiallylammonium (DADMAC), le chlorure d'acrylamidopropyltrimethylammonium (APTAC) et/ou le chlorure de methacrylamidopropyltrimethylammonium (MAPTAC), unsaturated cationic ethylenic monomer, preferably selected from the group consisting of dialkylaminoalkyl (meth) acrylamide, diallylamine, methyldiallylamine and their quaternary ammonium or acid salts. In particular, mention may be made of dimethyldiallylammonium chloride (DADMAC), acrylamidopropyltrimethylammonium chloride (APTAC) and / or methacrylamidopropyltrimethylammonium chloride (MAPTAC),
■ et/ou un monomère non ionique choisi préférentiellement dans le groupe comprenant le N-vinyl acetamide, N-vinyl formamide, la N- vinylpyrrolidone et/ou le vinyl acétate, ■ et/ou un monomère anionique de type acide ou anhydride choisi dans le groupe comprenant l'acide (méth)acrylique, l'acide acrylamidomethylpropyl sulfonique, l'acide itaconique, l'anhydride maléique, l'acide maléique, l'acide méthallyl sulfonique, l'acide vinylsulfonique et leurs sels. ■ and / or a nonionic monomer preferably selected from the group consisting of N-vinyl acetamide, N-vinylformamide, N-vinylpyrrolidone and / or vinyl acetate, ■ and / or an anionic monomer or acid anhydride selected from the group consisting of (meth) acrylic acid, sulfonic acrylamidomethylpropyl acid, itaconic acid, maleic anhydride, maleic acid, methallyl acid sulfonic acid, vinylsulfonic acid and their salts.
Avantageusement, le (co)polymère cationique ou amphotère final est issu de la réaction de préférence : Advantageously, the final cationic or amphoteric (co) polymer is derived from the reaction preferably:
15 à 25% massique de glyoxal,  15 to 25% by weight of glyoxal,
d'un (co)polymère base ramifié au moyen d'un agent ramifiant radicalaire et comprenant :  a branched (co) polymer base by means of a radical branching agent and comprising:
o au moins 5 moles % d'acrylamide,  at least 5 mole% of acrylamide,
o au moins 100 ppm de polyéthylèneimine,  at least 100 ppm of polyethyleneimine,
o 5 à 50 moles %, d'au moins un co-monomère éthylénique cationique non saturé, choisi dans le groupe comprenant les monomères de type dialkylaminoalkyl (meth)acrylamide, diallylamine, methyldiallylamine et leurs sel d'ammonium quaternaire ou d'acides, de préférence le chlorure de dimethyldiallylammonium,  5 to 50 mole%, of at least one unsaturated cationic ethylenic comonomer selected from the group consisting of dialkylaminoalkyl (meth) acrylamide, diallylamine, methyldiallylamine and their quaternary ammonium or acid salt monomers, preferably dimethyldiallylammonium chloride,
o Au moins 100 ppm d'un agent ramifiant radicalaire.  o At least 100 ppm of a radical branching agent.
II est important de noter que, en association avec ces monomères, il est également possible d'utiliser des monomères insolubles dans l'eau tels que les monomères acryliques, allyliques ou vinyliques comportant un groupement hydrophobe. Lors de leur utilisation, ces monomères seront employés dans des quantités très faibles, inférieures à 20 moles%, de préférence inférieures à 10 moles%, et ils seront choisis préférentiellement dans le groupe comprenant les dérivés de l'acrylamide comme les N-alkylacrylamide par exemple le N-tert-butylacrylamide, l'octylacrylamide ainsi que les Ν,Ν-dialkylacrylamides comme le Ν,Ν-dihexylacrylamide...les dérivés d'acide acrylique comme les alkyl acrylates et méthacrylates... It is important to note that, in combination with these monomers, it is also possible to use water-insoluble monomers such as acrylic, allylic or vinyl monomers having a hydrophobic group. When used, these monomers will be used in very small amounts, less than 20 mole%, preferably less than 10 mole%, and they will be chosen preferentially from the group comprising acrylamide derivatives such as N-alkylacrylamide by for example N-tert-butylacrylamide, octylacrylamide and Ν, Ν-dialkylacrylamides such as Ν, Ν-dihexylacrylamide ... acrylic acid derivatives such as alkyl acrylates and methacrylates ...
Selon un mode de réalisation préféré, le copolymère base mis en œuvre dans l'invention est un copolymère d'un monomère non ionique et d'un monomère cationique. L'incorporation du composé polyfonctionnel additionnel modifiant la structure du (co)polymère base pourra se faire dans le milieu réactionnel avant ou en cours de polymérisation, ou par tout autre méthode de greffage sur le copolymère base fini. De manière avantageuse, le composé polyfonctionnel ne réagit pas avec les monomères avant que ceux-ci ne soient polymérisés. According to a preferred embodiment, the base copolymer used in the invention is a copolymer of a nonionic monomer and a cationic monomer. The incorporation of the additional polyfunctional compound modifying the structure of the (co) polymer base can be done in the reaction medium before or during polymerization, or by any other grafting method on the finished base copolymer. Advantageously, the polyfunctional compound does not react with the monomers until they are polymerized.
De façon préférentielle, le composé polyfonctionnel additionnel sera mélangé à un comonomère avant polymérisation. Avantageusement, durant le procédé, la quantité de (co)polymère final introduite dans la suspension fibreuse est comprise entre 500 et 4000 grammes de polymère actif par tonne de pâte sèche (g/t). De préférence, la quantité introduite est comprise entre 1000 g/t et 3000 g/t. Le (co)polymère base ne nécessite pas le développement de procédé de polymérisation particulier. Les principales techniques de polymérisation, bien connues par l'homme de métier et pouvant être utilisées sont : la polymérisation par précipitation, la polymérisation en émulsion (aqueuse ou inverse) suivie ou non d'une étape de distillation et/ou de spray drying, et la polymérisation en suspension ou la polymérisation en solution, ces deux techniques étant préférées. Preferably, the additional polyfunctional compound will be mixed with a comonomer before polymerization. Advantageously, during the process, the amount of final (co) polymer introduced into the fibrous suspension is between 500 and 4000 grams of active polymer per tonne of dry pulp (g / t). Preferably, the quantity introduced is between 1000 g / t and 3000 g / t. The (co) polymer base does not require the development of a particular polymerization process. The main polymerization techniques, well known to those skilled in the art and which can be used are: precipitation polymerization, emulsion polymerization (aqueous or inverse) followed or not by a distillation step and / or spray drying, and suspension polymerization or solution polymerization, both of which are preferred.
La glyoxalation ne nécessite pas de méthode particulière. Les principales techniques de glyoxalation connues de l'homme de métier peuvent être utilisées. Par exemple, le pH pourra être ajusté après addition de glyoxal avec une solution de soude. Il est aussi possible de conduire la réaction à pH contrôlé par addition continue de soude, mais aussi d'additionner le glyoxal en plusieurs fractions. L'avancement de la réaction pourra aussi être suivi par une mesure de viscosité, de turbidité... etc. Glyoxalation does not require any particular method. The main glyoxalation techniques known to those skilled in the art can be used. For example, the pH may be adjusted after addition of glyoxal with a sodium hydroxide solution. It is also possible to conduct the reaction at controlled pH by continuous addition of sodium hydroxide, but also to add the glyoxal in several fractions. The progress of the reaction may also be followed by a measurement of viscosity, turbidity, etc.
Selon l'invention, l'additif est ajouté dans le procédé, avant ou après formation de la feuille. Ainsi, la mise en contact de la matière cellulosique avec l'additif peut être effectuée de différentes manières. Le (co)polymère final pourra être utilisé sous forme de solution aqueuse diluée ou non diluée. Il sera ajouté à la matière cellulosique. Il pourra être appliqué par une technique d'imprégnation, ou pourra être directement ajouté dans la suspension fibreuse à tout endroit du procédé de fabrication du papier où habituellement des agents de résistance à sec sont introduits. Il pourra être introduit dans la pâte épaisse (thick stock) ou dans la pâte diluée (thin stock). Il pourra être ajouté au niveau de la fan pump ou de la caisse de tête. Préférentiellement le (co)polymère sera introduit avant la caisse de tête. II pourra aussi être au niveau de la table de formation ou de la size presse, par exemple par spray. According to the invention, the additive is added to the process, before or after forming the sheet. Thus, the contacting of the cellulosic material with the additive can be carried out in different ways. The final (co) polymer may be used as a dilute or undiluted aqueous solution. It will be added to the cellulosic material. It may be applied by an impregnation technique, or may be added directly to the fibrous suspension at any point in the papermaking process where usually dry strength agents are introduced. It can be introduced into thick stock or thin stock. It can be added at the level of the fan pump or the headbox. Preferably the (co) polymer will be introduced before the headbox. It may also be at the level of the training table or press size, for example by spray.
L'incorporation ou l'application du (co)polymère final se fera avec les moyens conventionnels connus de l'homme de l'art. Incorporation or application of the final (co) polymer will be with conventional means known to those skilled in the art.
Préférentiellement, le (co)polymère final est injecté industriellement dans la suspension fibreuse, i.e. avant sa dilution par les eaux blanches (pâte épaisse). Les concentrations de la pâte sont de l'ordre de 3% et 5%. Le procédé pourra être utilisé avec des pâtes de fibres vierges (Kraft, Bisulfite..), de fibres recyclées, pâtes désencrées, pâtes mécaniques et thermo mécaniques. Preferably, the final (co) polymer is injected industrially into the fibrous suspension, i.e. before dilution with white water (thick paste). The concentrations of the dough are of the order of 3% and 5%. The process can be used with virgin fiber pulps (Kraft, Bisulfite ..), recycled fibers, de-inked pastes, mechanical and thermo mechanical pulps.
Le (co)polymère final pourra de manière être préparé à proximité de la machine à papier. The final (co) polymer may be prepared near the paper machine.
L'invention et les avantages qui en découlent ressort bien des exemples de réalisation suivants. The invention and the advantages that ensue from it are apparent from the following embodiments.
Exemples de réalisation Examples of realization
Protocole de synthèse du composé de l'invention Synthesis protocol of the compound of the invention
Synthèse du (co)polymère base modifié avec de la PEI pendant la polymérisation Les polymères de l'invention identifiés parmi les polymères 1 à 17 ont été obtenus à partir d'un copolymère base modifié avec de la PEI pendant la polymérisation selon le protocole suivant. Les exemples ont été effectués avec un copolymère acrylamide et chlorure de dimethyldiallyl ammonium (DADMAC), ramifié avec du MBA (1000 ppm / matière active), modifié avec un polymère de polyéthylèneimine (de type Polymin HM de BASF), à hauteur de 1% par rapport à la matière active. Pour ce faire, la polyéthylèneimine est mélangée au monomère de DADMAC et au MBA dans le réacteur. L'acrylamide sera incorporée en coulée continu pendant 2h, dans un milieu réactionnel maintenu à 85°C. La catalyse se fera au SPS et au MBS, catalyseurs bien connus de l'homme de métier. Synthèse du (co)polymère base avec post-greffage de la PEI Synthesis of PEI modified (co) polymer base during polymerization The polymers of the invention identified among polymers 1 to 17 were obtained from a PEI-modified base copolymer during polymerization according to the following protocol . The examples were carried out with a copolymer acrylamide and dimethyldiallyl ammonium chloride (DADMAC), branched with MBA (1000 ppm / active ingredient), modified with a polyethyleneimine polymer (BASF type Polymin HM), up to 1% compared to the active ingredient. To do this, the polyethyleneimine is mixed with the DADMAC monomer and the MBA in the reactor. The acrylamide will be incorporated in continuous casting for 2 hours, in a reaction medium maintained at 85 ° C. Catalysis will be SPS and MBS, catalysts well known to those skilled in the art. Synthesis of the (co) polymer base with post-grafting of the PEI
Dans le cas du post-greffage du (co)polymère les exemples (polymères 19 et 20) ont été effectués de la même manière que ci-dessus, à la différence que la polyéthylèneimine n'est pas mélangée au monomère dans le réacteur. Pour ce faire, la polyéthylèneimine est ajoutée dans le réacteur après la polymérisation à hauteur de 1% par rapport à la matière active. Le greffage se fait par catalyse à l'aide de 1500 ppm de SPS en coulée continue pendant lh30. In the case of the post-grafting of the (co) polymer, the examples (polymers 19 and 20) were carried out in the same manner as above, with the difference that the polyethyleneimine is not mixed with the monomer in the reactor. To do this, the polyethyleneimine is added to the reactor after the polymerization at a level of 1% relative to the active ingredient. The grafting is by catalysis using 1500 ppm of SPS in continuous casting for lh30.
Glyoxalation glyoxalation
Dans un réacteur agité de 600 ml, 154.3 g de copolymère base (20% de concentration, 3800 cps) et 626.6 g d'eau déminéralisée sont introduits. Le réacteur est équipé d'une sonde de mesure de pH. Après 10 minutes d'agitation le pH est ajusté à 10.5 avec une solution de soude à 10%. La température est maintenue entre 24 et 26°C. In a stirred reactor of 600 ml, 154.3 g of base copolymer (20% concentration, 3800 cps) and 626.6 g of demineralized water are introduced. The reactor is equipped with a pH sensor. After stirring for 10 minutes, the pH is adjusted to 10.5 with a 10% sodium hydroxide solution. The temperature is maintained between 24 and 26 ° C.
19.0 g de glyoxal à 40%> sont additionnés. La valeur de pH est de 8.75. Un contrôle du pH et un suivi de la viscosité permettent d'obtenir un produit de 52 cps après 65 minutes de réaction. Lorsque la viscosité souhaitée est atteinte, on stoppe la réaction par un abaissement du pH à moins de 3,5 par addition de H2S04 92%>. 19.0 g of 40% glyoxal are added. The pH value is 8.75. PH control and viscosity monitoring gave a product of 52 cps after 65 minutes of reaction. When the desired viscosity is reached, the reaction is stopped by lowering the pH to less than 3.5 by addition of 92% H 2 SO 4.
Le pH peut être ajusté après addition de glyoxal avec une solution de soude 10%>. Il est possible de conduire la réaction à pH contrôlé par addition continue de soude 10%>, mais aussi d'additionner le glyoxal en plusieurs fractions. Le viscosimètre utilisé est de type Brookfïeld, avec un module LV1 et une vitesse de 60 rpm. Préparation de la pâte The pH can be adjusted after adding glyoxal with 10% sodium hydroxide solution. It is possible to conduct the reaction at controlled pH by continuous addition of 10% sodium hydroxide, but also to add the glyoxal in several fractions. The viscometer used is Brookfield type, with a LV1 module and a speed of 60 rpm. Preparation of the dough
La pâte utilisée est constituée de fibres de cartons recyclées. La pâte à papier est préparée en désintégrant pendant 30 minutes 90 grammes de fibres recyclées dans 2 litres d'eau chaude. Le degré Shopper de la pâte ainsi obtenue est de 43. Les tests sont réalisés avec la pâte à pH neutre. La pâte obtenue est ensuite diluée jusqu'à un volume total de 9 litres. Une fois la consistance mesurée précisément, la quantité nécessaire de cette pâte est prélevée de manière à obtenir au final une feuille avec un grammage de 120g/m2. The paste used consists of recycled cardboard fibers. The pulp is prepared by disintegrating for 90 minutes 90 grams of recycled fibers in 2 liters of hot water. The Shopper degree of the dough thus obtained is 43. The tests are carried out with the paste at neutral pH. The paste obtained is then diluted to a total volume of 9 liters. Once the consistency measured accurately, the necessary amount of this paste is taken so as to ultimately obtain a sheet with a basis weight of 120g / m2.
Test des propriétés des polymères Testing the properties of polymers
AI Performances d'égouttage AI Drainage performance
Séquence CSF à 1000 rpm (tours par minute) :  CSF sequence at 1000 rpm (revolutions per minute):
Utilisation d'une formette statique pour réaliser l'agitation de la pâte. Introduction de 1 litre de pâte à 0,3 %. Use of a static form for stirring the dough. Introduction of 1 liter of paste at 0.3%.
T=0s : mise en agitation de la pâte T = 0s: agitation of the dough
T=10s : ajout du polymère T = 10s: addition of the polymer
T=30s : arrêt de l'agitation et récupération du litre de pâte. Réalisation du test TAPPI T 2270M-94.  T = 30s: Stopping the agitation and recovery of the liter of dough. Realization of the TAPPI T 2270M-94 test.
CSF : mesure du degré " d'égouttabillité " de la pâte CSF: measure of the degree of "draining" of the dough
B/ Performances en application DSR (résistance à sec), grammage à 60g/m2 B / Performance in DSR application (dry strength), grammage at 60g / m2
1/ Formation de la feuille 1 / Formation of the sheet
Les formettes de papier sont réalisées avec une formette dynamique automatique. La pâte est introduite dans le cuvier de la formette dynamique, diluée jusqu'à une consistance de 0,32% et agitée modérément avec un agitateur mécanique afin d'homogénéiser la suspension fibreuse. En mode manuel, la pâte est pompée jusqu'au niveau de la buse afin d'amorcer le circuit. Un buvard et la toile de formation sont placés dans le bol de la formette dynamique avant de démarrer la rotation du bol à 900m/min et de construire le mur d'eau. Le copolymère final est alors introduit dans la suspension fibreuse agitée avec un temps de contact de 30 secondes.. La feuille est alors réalisée (en mode automatique) par 22 allers-retours de la buse projetant la pâte dans le mur d'eau. Une fois que l'eau est drainée et que la séquence automatique est terminée, la toile de formation avec le réseau de fibres formé est retirée du bol de la formette dynamique et placée sur une table. Un buvard sec est déposé du côté du matelas de fibres humides et est pressé une fois avec un rouleau. L'ensemble est retourné et la toile est délicatement séparée du matelas fibreux. Un second buvard sec est déposé et la feuille (entre les deux buvards) est pressée une fois sous une presse délivrant 4 bars puis est séchée sur un sécheur tendu pendant 9 min à 107°C. Les deux buvards sont ensuite retirés et la feuille est stockée pendant une nuit dans une pièce à humidité et température contrôlées (50% d'humidité relative et 23 °C). Les propriétés de résistance à sec de toutes les feuilles obtenues par cette procédure sont alors évaluées. The paper forms are made with an automatic dynamic form. The paste is introduced into the cuvier of the dynamic form, diluted to a consistency of 0.32% and stirred moderately with a mechanical stirrer to homogenize the fibrous suspension. In manual mode, the dough is pumped to the nozzle level to prime the circuit. A blotter and training cloth are placed in the bowl of the dynamic formette before starting the rotation of the bowl at 900m / min and constructing the water wall. The final copolymer is then introduced into the stirred fibrous suspension with a contact time of 30 seconds. The sheet is then made (in automatic mode) by 22 round-trips of the nozzle projecting the paste in the wall of water. Once the water is drained and the automatic sequence is complete, the forming web with the formed fiber network is removed from the dynamically shaped bowl and placed on a table. A dry blotter is deposited on the side of the wet fiber mat and is pressed once with a roll. The whole is returned and the fabric is delicately separated from the fibrous mat. A second dry blotter is deposited and the sheet (between the two blotters) is pressed once under a press delivering 4 bars and is then dried on a dryer stretched for 9 min at 107 ° C. The two blotters are then removed and the sheet is stored overnight in a room with controlled humidity and temperature (50% relative humidity and 23 ° C). The dry strength properties of all the sheets obtained by this procedure are then evaluated.
21 Test d'éclatement L'éclatement (Burst index) est mesuré avec un éclatomètre Messmer Buchel M 405 (moyenne sur 14 mesures). Le test est effectué selon la norme TAPPI T403 OM 91 21 Burst test Burst index is measured with a Messmer Buchel M 405 burst (average of 14 measurements). The test is performed according to TAPPI standard T403 OM 91
3/ Test de traction à sec La longueur de rupture est mesurée à l'aide d'un dynamomètre testometric AXM250. Le test est effectué selon la norme TAPPI 494 OM 88. 3 / Dry tensile test The fracture length is measured using an AXM250 testometric dynamometer. The test is performed according to the TAPPI 494 OM 88 standard.
Cas du (co)polymère base modifié avec de la PEI pendant la polymérisation  Case of (base) polymer modified with PEI during polymerization
Dans tous les exemples qui suivent, et sauf indication contraire, les feuilles de papier sont réalisées selon la procédure ci-dessus en introduisant le copolymère final à un dosage de 2.5 kg/T (polymère sec / fibre sèche). In all the examples which follow, and unless otherwise indicated, the sheets of paper are made according to the above procedure by introducing the final copolymer at a dosage of 2.5 kg / T (dry polymer / dry fiber).
La ramification seule du copolymère base glyoxalé et dépourvu de PEI (polymère 3) permet d'obtenir une amélioration des performances d'égouttage, mais est préjudiciable à l'amélioration des propriétés physiques. Le procédé de l'invention permet, quant à lui d'obtenir une amélioration de l'égouttage supérieur aux autres produits tout en conservant, voire même tout en améliorant les propriétés physiques à sec. The branching alone of the glyoxalated base copolymer and free of PEI (polymer 3) makes it possible to obtain an improvement in drainage performance, but is detrimental to the improvement of the physical properties. The method of the invention makes it possible to obtain an improvement of drainage superior to other products while maintaining or even while improving the dry physical properties.
1000* PEI additionnée au copolymère ayant réagi avec le composé aldéhyde. 1000 * PEI added to the copolymer reacted with the aldehyde compound.
1000** PEI additionnée au copolymère avant réaction avec le composé aldéhyde. Il ne s'agit pas d'un greffage nécessitant des conditions réactionnelles spécifiques. La PEI est simplement mélangée avec le copolymère.  1000 ** PEI added to the copolymer before reaction with the aldehyde compound. It is not a grafting requiring specific reaction conditions. The PEI is simply mixed with the copolymer.
Cette seconde série d'essais démontre que la tendance d'amélioration des résultats reste identique lors de l'utilisation de copolymères base de plus basse viscosité (polymères 5 et 6). Les résultats obtenus avec le polymère 8a et 8b sont inférieurs à ceux du polymère de l'invention. Ces résultats démontrent l'importance de la présence de la PEI lors de la polymérisation du copolymère base et son incorporation dans la structure du copolymère base. This second series of tests shows that the trend of improving the results remains the same when using lower viscosity base copolymers (polymers 5 and 6). The results obtained with the polymer 8a and 8b are lower than those of the polymer of the invention. These results demonstrate the importance of the presence of PEI during the polymerization of the base copolymer and its incorporation into the structure of the base copolymer.
Le tableau ci-dessus montre l'évolution des résultats par rapport à l'augmentation de la cationicité du polymère base. Les polymères de l'invention sont tous meilleurs que le polymère 9. The table above shows the evolution of the results with respect to the increase of the cationicity of the base polymer. The polymers of the invention are all better than the polymer 9.
En comparant les performances des polymères 9 et 10 de même cationicité, on observe de façon surprenante qu'avec un poids moléculaire plus bas dans le cadre de l'invention (polymère 10), on peut obtenir des meilleurs résultats d'égouttage et de résistance à sec. Comparing the performance of polymers 9 and 10 of the same cationicity, it is surprisingly observed that with a lower molecular weight within the scope of the invention (polymer 10), better drainage and resistance results can be obtained. dried up.
Avec un poids moléculaire similaire (copolymère base), les polymères 10 et 14 présentent des performances différentes. Le polymère 14, qui a une cationicité de 40 mole%, donne des résultats supérieurs que ce soit en égouttage ou éclatement (Burst Index) au polymère 10 (5 mole% de cationicité). With a similar molecular weight (base copolymer), polymers 10 and 14 exhibit different performance. Polymer 14, which has a cationicity of 40 mole%, gives superior results whether in drip or burst (Burst Index) to polymer 10 (5 mole% cationicity).
Il convient de noter que le bénéfice de l'invention s'applique quelle que soit la cationicité du produit. En effet, en comparant les polymères 12 et 13, tous deux de même cationicité (30 mole%), on constate que le polymère de l'invention (polymère 12) donne les meilleures performances d'égouttage et de propriétés physiques. It should be noted that the benefit of the invention applies regardless of the cationicity of the product. Indeed, by comparing the polymers 12 and 13, both of the same cationicity (30 mol%), it is found that the polymer of the invention (polymer 12) gives the best performance of dripping and physical properties.
Le polymère 17 correspond à l'exemple 7 du brevet US20110056640 qui a été reproduit puis testé. The polymer 17 corresponds to Example 7 of the patent US20110056640 which was reproduced and then tested.
Le tableau ci-dessus montre que deux polymères (polymères 15 et 16) issus de l'invention, glyoxalés à deux viscosités différentes, présentent des performances supérieures au polymère 17, de même cationicité. Cas du (co)polymère base modifié avec de la PEI par post-greffage The above table shows that two polymers (polymers 15 and 16) from the invention, glyoxalized at two different viscosities, have superior performance to polymer 17, the same cationicity. Case of the base (co) polymer modified with PEI by post-grafting
Les polymères 19 et 20 ont été fabriqués à partir du (co)polymère base avec post-greffage de la PEI. Plus précisément, on effectue la polymérisation de l'acrylamide et du DADMAC en présence de MBA. Le polymère obtenu est alors séparé en trois fractions. Polymers 19 and 20 were made from the (co) polymer base with post-grafting of PEI. More specifically, the polymerization of acrylamide and DADMAC is carried out in the presence of MBA. The polymer obtained is then separated into three fractions.
La première fraction réagit avec le glyoxal de la façon décrite précédemment : échantillon 18. The first fraction reacts with glyoxal as previously described: Sample 18.
Dans la deuxième fraction, on ajoute de la PEI ainsi qu'un initiateur (SPS), en coulée continue durant 90 minutes à 80°C, dans le but de post-greffer la PEI. Cet échantillon a été glyoxalé selon le processus standard: Echantillon 19. In the second fraction, PEI and an initiator (SPS) are added in continuous casting for 90 minutes at 80 ° C for the purpose of post-grafting the PEI. This sample was glyoxalized according to the standard process: Sample 19.
La troisième fraction a été traitée de la même façon que pour l'échantillon 19, mais sans l'addition de la PEI. Le but est d'évaluer l'impact de l'addition en continue du SPS. La gloxalation est identique aux exemples 18 et 19. The third fraction was treated in the same way as for sample 19, but without the addition of PEI. The goal is to evaluate the impact of the continuous addition of the SPS. Gloxalation is identical to Examples 18 and 19.
Les résultats (égouttage au CSF) montrent un gain de performance si l'on compare le polymère 18 (base sans PEI) et le polymère 19 (base PEI post- greffée). Le polymère 20 a des performances inférieures au polymère 18, signe d'une dégradation du polymère lors de l'addition du SPS durant 90 minutes à 80°C. C'est donc bien le post-greffage de la PEI qui apporte ce gain en performance. The results (CSF dewatering) show a gain in performance when comparing the polymer 18 (base without PEI) and the polymer 19 (post-grafted PEI base). Polymer 20 has lower performance than polymer 18, a sign of polymer degradation upon addition of SPS for 90 minutes at 80 ° C. It is thus the post-grafting of the PEI that brings this gain in performance.

Claims

REVENDICATIONS
1/ Procédé de fabrication d'une feuille de papier et/ou de carton et analogues, selon lequel, avant ou après formation de ladite feuille, on met en contact la matière cellulosique avec au moins un additif, caractérisé en ce que ledit additif est un (co)polymère cationique ou amphotère issu de la réaction entre au moins un aldéhyde et au moins un (co)polymère base comprenant au moins un monomère non ionique choisi dans le groupe comprenant l'acrylamide (et/ou le méthacrylamide), le N,N diméthylacrylamide, et/ou l'acrylonitrile, ledit copolymère base étant préalablement modifié avec au moins un composé polyfonctionnel comprenant au moins 3 hétéroatomes choisis parmi N, S, O, P, dont au moins 3 de ces hétéroatomes présentent chacun au moins un hydrogène mobile 1 / A method of manufacturing a sheet of paper and / or cardboard and the like, according to which, before or after formation of said sheet, the cellulosic material is brought into contact with at least one additive, characterized in that said additive is a cationic or amphoteric (co) polymer resulting from the reaction between at least one aldehyde and at least one (co) polymer base comprising at least one nonionic monomer chosen from the group comprising acrylamide (and / or methacrylamide), N, N-dimethylacrylamide, and / or acrylonitrile, said base copolymer being previously modified with at least one polyfunctional compound comprising at least 3 heteroatoms chosen from N, S, O, P, at least 3 of which are each heteroatoms each a mobile hydrogen
2/ Procédé selon la revendication 1, caractérisé en ce que le (co)polymère base est modifié avec au moins un composé polyfonctionnel soit par incorporation de(s) composé(s) polyfonctionnel(s) additionnel(s) avant ou pendant la polymérisation des co-monomères constitutifs du (co)polymère base, soit par greffage de(s) composé(s) polyfonctionnel(s) additionnel(s) sur le (co)polymère base. 3/ Procédé selon l'une des revendications précédentes, caractérisé en ce que le(s) composé(s) polyfonctionnel(s) sont choisis dans le groupe comprenant les polyethylèneimines (PEI), les polyamines (primaires et secondaires), les polyallyamines, les polythiols, les polyalcools, les polyamides epichlorhydrine (PAE), les polyamines amides (PAA), 2 / A method according to claim 1, characterized in that the (co) polymer base is modified with at least one polyfunctional compound or by incorporation of (s) polyfunctional compound (s) additional (s) before or during the polymerization constituent comonomers of the (co) polymer base, either by grafting additional polyfunctional compound (s) onto the (co) polymer base. 3 / A method according to one of the preceding claims, characterized in that the (s) compound (s) polyfunctional (s) are selected from the group comprising polyethyleneimines (PEI), polyamines (primary and secondary), polyallyamines, polythiols, polyalcohols, polyamides epichlorohydrin (PAE), polyamines amides (PAA),
4/ Procédé selon la revendication 3, caractérisé en ce que le composé polyfonctionnel est choisi dans le groupe comprenant la polyéthylèneimine (PEI) et la polyamine amide (PAA). 5/ Procédé selon l'une des revendications précédentes, caractérisé en ce que le copolymère base est ramifié en présence d'un agent ramifiant radicalaire. 4 / A method according to claim 3, characterized in that the polyfunctional compound is selected from the group comprising polyethyleneimine (PEI) and polyamine amide (PAA). 5 / A method according to one of the preceding claims, characterized in that the base copolymer is branched in the presence of a radical branching agent.
6/ Procédé selon la revendication 5, caractérisé en ce que l'agent ramifiant radicalaire est choisi dans le groupe comprenant le méthylène bisacrylamide (MBA), l'ethylene glycol di-acrylate, le polyethylene glycol dimethacrylate, le diacrylamide, le cyanomethylacrylate, le vinyloxyethylacrylate ou methacrylate, la trially lamine. 7/ Procédé selon l'une des revendications précédentes, caractérisé en ce que l'aldéhyde est choisi parmi le glyoxal, le glutaraldéhyde, le furane-dialdéhyde, le 2- hydroxyadipaldéhyde, le succinaldéhyde, le dialdéhyde amidon, le 2,2 dimethoxyethanal, les composés diépoxy, et leurs combinaisons. 6 / A method according to claim 5, characterized in that the radical branching agent is selected from the group comprising methylene bisacrylamide (MBA), ethylene glycol di-acrylate, polyethylene glycol dimethacrylate, diacrylamide, cyanomethylacrylate, vinyloxyethylacrylate or methacrylate, trially lamine. 7 / A method according to one of the preceding claims, characterized in that the aldehyde is chosen from glyoxal, glutaraldehyde, furan-dialdehyde, 2-hydroxyadipaldehyde, succinaldehyde, dialdehyde starch, 2,2-dimethoxyethanal, diepoxy compounds, and combinations thereof.
8/ Procédé selon la revendication 7, caractérisé en ce que l'aldéhyde est le glyoxal. 8 / A method according to claim 7, characterized in that the aldehyde is glyoxal.
9/ Procédé selon l'une des revendications 1 à 7, caractérisé en ce que le (co)polymère cationique ou amphotère est issu de la réaction entre: 9 / A method according to one of claims 1 to 7, characterized in that the cationic or amphoteric (co) polymer is derived from the reaction between:
de 1 à 30% massique d'au moins un aldéhyde choisi dans le groupe comprenant le glyoxal, le glutaraldéhyde, le furane-dialdéhyde, le 2-hydroxyadipaldéhyde, le succinaldéhyde, le dialdéhyde amidon, le 2,2 dimethoxyethanal, les composés diépoxy, et leurs combinaisons,  from 1 to 30% by weight of at least one aldehyde selected from the group consisting of glyoxal, glutaraldehyde, furan-dialdehyde, 2-hydroxyadipaldehyde, succinaldehyde, dialdehyde starch, 2,2-dimethoxyethanal, diepoxy compounds, and their combinations,
avec au moins un (co)polymère base éventuellement ramifié au moyen d'un agent ramifiant radicalaire et contenant :  with at least one (co) polymer base optionally branched by means of a radical branching agent and containing:
o au moins 5 moles % d'un monomère non ionique choisi dans le groupe comprenant l'acrylamide (et/ou le méthacrylamide), le N, N diméthylacrylamide et/ou l'acrylonitrile,  at least 5 mole% of a nonionic monomer chosen from the group comprising acrylamide (and / or methacrylamide), N, N-dimethylacrylamide and / or acrylonitrile,
o au moins 100 ppm d'au moins un composé polyfonctionnel additionnel choisi dans le groupe comprenant polyéthylèneimine, polyamine (primaire ou secondaire), polyallylamine, polythiols, les polyalcools, polyamides epichlorhydrine (PAE), polyamines amides (PAA) avantageusement polyéthylèneimine,  at least 100 ppm of at least one additional polyfunctional compound chosen from the group comprising polyethyleneimine, polyamine (primary or secondary), polyallylamine, polythiols, polyalcohols, polyamides epichlorohydrin (PAE), polyamine amides (PAA), advantageously polyethyleneimine,
o optionnellement au moins :  o optionally at least:
■ un monomère éthylénique cationique non saturé, choisi dans le groupe comprenant les monomères de type dialkylaminoalkyl (meth)acrylamide, diallylamine, methyldiallylamine et leurs sel d'ammonium quaternaire ou d'acides, et en particulier le chlorure de dimethyldiallylammonium (DADMAC), le chlorure d'acrylamidopropyltrimethylammonium (APTAC) et/ou le chlorure de methacrylamidopropyltrimethylammonium (MAPTAC), ■ et/ou un monomère non ionique choisi dans le groupe comprenant le N-vinyl acetamide, N-vinyl formamide, la N- vinylpyrrolidone et/ou le vinyl acétate, ■ et/ou un monomère anionique de type acide ou anhydride choisi dans le groupe comprenant l'acide (méth)acrylique, l'acide acrylamidomethylpropyl sulfonique, l'acide itaconique, l'anhydride maléique, l'acide maléique, l'acide méthallyl sulfonique, l'acide vinylsulfonique et leurs sels. An unsaturated cationic ethylenic monomer selected from the group consisting of dialkylaminoalkyl (meth) acrylamide, diallylamine, methyldiallylamine and their quaternary ammonium or acid salts, and in particular dimethyldiallylammonium chloride (DADMAC), acrylamidopropyltrimethylammonium chloride (APTAC) and / or methacrylamidopropyltrimethylammonium chloride (MAPTAC), and / or a nonionic monomer selected from the group consisting of N-vinylacetamide, N-vinylformamide, N-vinylpyrrolidone and / or vinyl acetate, ■ and / or an anionic monomer or acid anhydride selected from the group consisting of (meth) acrylic acid, sulfonic acrylamidomethylpropyl acid, itaconic acid, maleic anhydride, maleic acid, methallyl acid sulfonic acid, vinylsulfonic acid and their salts.
10/ Procédé selon l'une des revendications 1 à 8, caractérisé en ce que le (co)polymère cationique ou amphotère final est issu de la réaction de préférence : 10 / A method according to one of claims 1 to 8, characterized in that the final cationic or amphoteric (co) polymer is derived from the reaction preferably:
15 à 25% massique de glyoxal,  15 to 25% by weight of glyoxal,
d'un (co)polymère base ramifié au moyen d'un agent ramifiant radicalaire et comprenant :  a branched (co) polymer base by means of a radical branching agent and comprising:
o au moins 5 moles % d'acrylamide,  at least 5 mole% of acrylamide,
o au moins 100 ppm de polyéthylèneimine,  at least 100 ppm of polyethyleneimine,
o 5 à 50 moles %, d'au moins un co-monomère éthylénique cationique non saturé, choisi dans le groupe comprenant les monomères de type dialkylaminoalkyl (meth)acrylamide, diallylamine, methyldiallylamine et leurs sel d'ammonium quaternaire ou d'acides, de préférence le chlorure de dimethyldiallylammonium,  5 to 50 mole%, of at least one unsaturated cationic ethylenic comonomer selected from the group consisting of dialkylaminoalkyl (meth) acrylamide, diallylamine, methyldiallylamine and their quaternary ammonium or acid salt monomers, preferably dimethyldiallylammonium chloride,
o Au moins 100 ppm d'un agent ramifiant radicalaire.  o At least 100 ppm of a radical branching agent.
EP13712850.0A 2012-02-27 2013-02-26 Novel method for producing paper implementing a base copolymer having reacted with an aldehyde as a dry strength, retention, drainage and machinability agent Active EP2820188B1 (en)

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FR2987375A1 (en) 2012-02-27 2013-08-30 Snf Sas NOVEL PAPERMAKING PROCESS USING A BASIC COPOLYMER HAVING REACTED WITH ALDEHYDE AS DRY RESISTANCE, RETENTION, DRIP, AND MACHINABILITY AGENT

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CA2862995A1 (en) 2013-09-06
US20150136348A1 (en) 2015-05-21
WO2013128109A1 (en) 2013-09-06
ES2609676T3 (en) 2017-04-21
BR112014017918A2 (en) 2020-06-23
CN104093900A (en) 2014-10-08
CA2862995C (en) 2020-06-02
KR102157401B1 (en) 2020-09-17
FR2987375A1 (en) 2013-08-30
BR112014017918B1 (en) 2021-06-01
EP2820188B1 (en) 2016-12-07
KR20140138117A (en) 2014-12-03
US9506200B2 (en) 2016-11-29
US10132039B2 (en) 2018-11-20
CN104093900B (en) 2016-09-21
US20170037575A1 (en) 2017-02-09

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